Fast-growing poplar wood is limited by poor dimensional stability and biological durability, while conventional treatment methods (such as involving toxic wood preservatives) often raise environmental and health concerns. Furthermore, some emerging chemical modification techniques, such as acetylation and furfurylation, are relatively expensive, which increases the final product cost. To address these challenges, we propose a bio-based sustainable approach: impregnating poplar wood with a hybrid system (GCA) composed of two lower-cost bio-based chemicals, citric acid (CA) and glycerol (G), to induce in-situ esterification without generating harmful by-products. The modification mechanism involves the formation of a robust, cross-linked GCA polyester network within the wood cell wall, leading to comprehensive performance enhancements. The dimensional stability was substantially improved, with a 64% anti-swelling efficiency. This is primarily attributed to the network restricting the wood’s interaction with moisture, particularly cell-wall-associated bound water, as confirmed by LFNMR analysis. The reinforcing network also significantly enhanced mechanical properties, including a 65% increase in modulus of elasticity and a 57% increase in compressive strength. Moreover, the GCA-modified wood demonstrated exceptional durability, exhibiting enhanced ultraviolet resistance with greater color stability, a remarkable reduction in mass loss against decay fungi, and complete inhibition of mold growth. This environmentally friendly and effective strategy presents a promising pathway for converting low-grade wood into a high-performance, durable material suitable for demanding construction and outdoor applications.